US5063262A - Polymeric costabilizers for molding compositions based on polymers of vinyl chloride - Google Patents
Polymeric costabilizers for molding compositions based on polymers of vinyl chloride Download PDFInfo
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- US5063262A US5063262A US07/588,938 US58893890A US5063262A US 5063262 A US5063262 A US 5063262A US 58893890 A US58893890 A US 58893890A US 5063262 A US5063262 A US 5063262A
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- 239000000203 mixture Substances 0.000 title claims abstract description 55
- 229920000642 polymer Polymers 0.000 title claims abstract description 23
- 238000000465 moulding Methods 0.000 title claims description 10
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title abstract description 6
- 239000003381 stabilizer Substances 0.000 claims abstract description 64
- 229920001577 copolymer Polymers 0.000 claims abstract description 15
- 238000009757 thermoplastic moulding Methods 0.000 claims abstract description 12
- 229920000765 poly(2-oxazolines) Polymers 0.000 claims abstract description 7
- 239000011701 zinc Substances 0.000 claims description 85
- 125000004432 carbon atom Chemical group C* 0.000 claims description 42
- 150000001875 compounds Chemical class 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 125000004122 cyclic group Chemical group 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000002252 acyl group Chemical group 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 229920005862 polyol Polymers 0.000 claims description 4
- 150000003077 polyols Chemical class 0.000 claims description 4
- 125000001931 aliphatic group Chemical class 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000006356 alkylene carbonyl group Chemical group 0.000 claims description 3
- 125000005529 alkyleneoxy group Chemical group 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 235000013877 carbamide Nutrition 0.000 claims description 2
- 150000002475 indoles Chemical class 0.000 claims description 2
- 150000003217 pyrazoles Chemical class 0.000 claims description 2
- 150000003585 thioureas Chemical class 0.000 claims description 2
- 150000003672 ureas Chemical class 0.000 claims description 2
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims 2
- 125000006165 cyclic alkyl group Chemical class 0.000 claims 2
- 101150108015 STR6 gene Proteins 0.000 claims 1
- 150000001912 cyanamides Chemical class 0.000 claims 1
- 150000002989 phenols Chemical class 0.000 claims 1
- 150000003752 zinc compounds Chemical class 0.000 abstract description 5
- 230000000087 stabilizing effect Effects 0.000 abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 2
- 150000002918 oxazolines Chemical class 0.000 abstract description 2
- -1 cadmium carboxylates Chemical class 0.000 description 116
- 229920006187 aquazol Polymers 0.000 description 42
- 238000009472 formulation Methods 0.000 description 19
- 230000008642 heat stress Effects 0.000 description 18
- 239000004800 polyvinyl chloride Substances 0.000 description 11
- 229920000915 polyvinyl chloride Polymers 0.000 description 11
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 10
- 235000021355 Stearic acid Nutrition 0.000 description 9
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 9
- 239000008117 stearic acid Substances 0.000 description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical class [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 7
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 5
- 239000012170 montan wax Substances 0.000 description 5
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000005711 Benzoic acid Substances 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- 235000010233 benzoic acid Nutrition 0.000 description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- GZQKJQLFIGBEIE-UHFFFAOYSA-N 2-[4-(4,5-dihydro-1,3-oxazol-2-yl)butyl]-4,5-dihydro-1,3-oxazole Chemical compound N=1CCOC=1CCCCC1=NCCO1 GZQKJQLFIGBEIE-UHFFFAOYSA-N 0.000 description 2
- NYEZZYQZRQDLEH-UHFFFAOYSA-N 2-ethyl-4,5-dihydro-1,3-oxazole Chemical compound CCC1=NCCO1 NYEZZYQZRQDLEH-UHFFFAOYSA-N 0.000 description 2
- GUXJXWKCUUWCLX-UHFFFAOYSA-N 2-methyl-2-oxazoline Chemical compound CC1=NCCO1 GUXJXWKCUUWCLX-UHFFFAOYSA-N 0.000 description 2
- FVEZUCIZWRDMSJ-UHFFFAOYSA-N 2-propan-2-yl-4,5-dihydro-1,3-oxazole Chemical compound CC(C)C1=NCCO1 FVEZUCIZWRDMSJ-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 244000068988 Glycine max Species 0.000 description 2
- 235000010469 Glycine max Nutrition 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- VACHUYIREGFMSP-UHFFFAOYSA-N (+)-threo-9,10-Dihydroxy-octadecansaeure Natural products CCCCCCCCC(O)C(O)CCCCCCCC(O)=O VACHUYIREGFMSP-UHFFFAOYSA-N 0.000 description 1
- NMBZRXYPTRKTCN-UHFFFAOYSA-N (2,4-ditert-butylphenyl) didodecyl phosphite Chemical compound CCCCCCCCCCCCOP(OCCCCCCCCCCCC)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C NMBZRXYPTRKTCN-UHFFFAOYSA-N 0.000 description 1
- QIBOWVKBPQNSBZ-UHFFFAOYSA-N (2,6-ditert-butylphenyl) didodecyl phosphite Chemical compound CCCCCCCCCCCCOP(OCCCCCCCCCCCC)OC1=C(C(C)(C)C)C=CC=C1C(C)(C)C QIBOWVKBPQNSBZ-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- JPFGKGZYCXLEGQ-UHFFFAOYSA-N 1-(4-methoxyphenyl)-5-methylpyrazole-4-carboxylic acid Chemical compound C1=CC(OC)=CC=C1N1C(C)=C(C(O)=O)C=N1 JPFGKGZYCXLEGQ-UHFFFAOYSA-N 0.000 description 1
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical group CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 1
- LRQGFQDEQPZDQC-UHFFFAOYSA-N 1-Phenyl-1,3-eicosanedione Chemical compound CCCCCCCCCCCCCCCCCC(=O)CC(=O)C1=CC=CC=C1 LRQGFQDEQPZDQC-UHFFFAOYSA-N 0.000 description 1
- LUBJCRLGQSPQNN-UHFFFAOYSA-N 1-Phenylurea Chemical compound NC(=O)NC1=CC=CC=C1 LUBJCRLGQSPQNN-UHFFFAOYSA-N 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical group CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical group CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical group CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical class CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- OYYXZGFIZTYYRB-UHFFFAOYSA-N 2-octyldecanoic acid Chemical compound CCCCCCCCC(C(O)=O)CCCCCCCC OYYXZGFIZTYYRB-UHFFFAOYSA-N 0.000 description 1
- KLLLJCACIRKBDT-UHFFFAOYSA-N 2-phenyl-1H-indole Chemical compound N1C2=CC=CC=C2C=C1C1=CC=CC=C1 KLLLJCACIRKBDT-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical class CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- FYYGCTQPBDNICZ-UHFFFAOYSA-N 2-tetradecyloctadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(C(O)=O)CCCCCCCCCCCCCC FYYGCTQPBDNICZ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- FLZYQMOKBVFXJS-UHFFFAOYSA-N 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoic acid Chemical compound CC1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O FLZYQMOKBVFXJS-UHFFFAOYSA-N 0.000 description 1
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- KDVYCTOWXSLNNI-UHFFFAOYSA-N 4-t-Butylbenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1 KDVYCTOWXSLNNI-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- VACHUYIREGFMSP-SJORKVTESA-N 9,10-Dihydroxystearic acid Natural products CCCCCCCC[C@@H](O)[C@@H](O)CCCCCCCC(O)=O VACHUYIREGFMSP-SJORKVTESA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 239000004801 Chlorinated PVC Substances 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 239000004908 Emulsion polymer Substances 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000004450 alkenylene group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- LKAVYBZHOYOUSX-UHFFFAOYSA-N buta-1,3-diene;2-methylprop-2-enoic acid;styrene Chemical compound C=CC=C.CC(=C)C(O)=O.C=CC1=CC=CC=C1 LKAVYBZHOYOUSX-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- YFNONBGXNFCTMM-UHFFFAOYSA-N butoxybenzene Chemical group CCCCOC1=CC=CC=C1 YFNONBGXNFCTMM-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000853 cresyl group Chemical group C1(=CC=C(C=C1)C)* 0.000 description 1
- 125000004977 cycloheptylene group Chemical group 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- 125000004978 cyclooctylene group Chemical group 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000004979 cyclopentylene group Chemical group 0.000 description 1
- 125000005534 decanoate group Chemical class 0.000 description 1
- 125000003493 decenyl group Chemical group [H]C([*])=C([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- ZOQOJLXIMYWJPF-UHFFFAOYSA-N didecyl (2-nonylphenyl) phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC ZOQOJLXIMYWJPF-UHFFFAOYSA-N 0.000 description 1
- NMAKPIATXQEXBT-UHFFFAOYSA-N didecyl phenyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OC1=CC=CC=C1 NMAKPIATXQEXBT-UHFFFAOYSA-N 0.000 description 1
- 125000004925 dihydropyridyl group Chemical group N1(CC=CC=C1)* 0.000 description 1
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000000687 hydroquinonyl group Chemical class C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical class CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical class CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical class CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 150000002942 palmitic acid derivatives Chemical class 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000004707 phenolate Chemical class 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical class CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- 125000005063 tetradecenyl group Chemical group C(=CCCCCCCCCCCCC)* 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- KFUSEUYYWQURPO-OWOJBTEDSA-N trans-1,2-dichloroethene Chemical compound Cl\C=C\Cl KFUSEUYYWQURPO-OWOJBTEDSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- FICPQAZLPKLOLH-UHFFFAOYSA-N tricyclohexyl phosphite Chemical compound C1CCCCC1OP(OC1CCCCC1)OC1CCCCC1 FICPQAZLPKLOLH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/12—Polyester-amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/02—Polyamines
Definitions
- the present invention stabilized thermoplastic molding compositions based on halogen-containing polymers, in particular polyvinyl chloride or polymers essentially containing vinyl chloride, and costabilizers for preparing such compositions.
- chloride-containing polymers are readily degraded by the action of heat, for example, during processing. This degradation leads to undesired discolorations and to an impairment of the mechanical properties. Consequently, this degradation is avoided by adding stabilizers to the polymers before processing.
- stabilizers In the case of polyvinyl chloride and copolymers containing essentially vinyl chloride, particular use is made of organotin compounds, inorganic and organic lead salts, organic antimony compounds or combinations of cadmium carboxylates and barium carboxylates and also of a mixture of zinc soaps and polyoxazolines. These so-called primary stabilizers are frequently supplemented with costabilizers to improve their effectiveness.
- costabilizers which improve the initial color and the ultimate stability of the chlorine-containing polymer.
- epoxy compounds, polyols, organic phosphites, substituted dihydropyridines, 1,3-diketones or combinations of these compounds are used.
- one object of this invention is to provide costabilizers which enhance the heat-stabilizing action of stabilizers.
- thermoplastic molding compositions which contain a costabilizer which enhances the heat-stabilizing action of stabilizers.
- thermoplastic molding compositions which contain a costabilizer which enhances the heat-stabilizing action of primary polymeric stabilizers.
- thermoplastic molding compositions based on halogen-containing polymers which contain a stabilizer and a costabilizer which enhances the heat-stabilizing action of the stabilizer.
- FIGS. 1, 7, 10 and 11 graphically illustrate the heat-stabilizing effect of various stabilizers in various thermoplastic molding compositions by plotting the Yellowness Index (YI) as a function of the time of heat stress, for the stabilizers: Zn/PX ( ⁇ ), Zn/PX/TMP (+), Zn/PX/Cop (*) and Zn/PX/TMP/Cop ( ⁇ );
- YI Yellowness Index
- FIGS. 2, 8, 9 and 12 graphically illustrate the heat-stabilizing effect of various stabilizers in various thermoplastic molding compositions by plotting the Yellowness Index (YI) as a function of the time of heat stress, for the stabilizers: Zn/PC ( ⁇ ), Zn/PC/TMP (+), Zn/PC/Cop (*) and Zn/PC/TMP/Cop ( ⁇ );
- YI Yellowness Index
- FIG. 3 graphically illustrates the heat-stabilizing effect of various stabilizers in a thermoplastic molding composition by plotting the Yellowness Index (YI) as a function of the time of heat stress, for the stabilizers Zn/PC ( ⁇ ) and Zn/PC/Cop (*);
- YI Yellowness Index
- FIG. 4 graphically illustrates the heat-stabilizing effect of various stabilizers in a thermoplastic molding composition by plotting the Yellowness Index (YI) as a function of the time of heat stress, for the stabilizers: Zn/PC/TMP (+) and Zn/PC/TMP/Cop ( ⁇ );
- YI Yellowness Index
- FIG. 5 graphically illustrates the heat-stabilizing effect of various stabilizers in a thermoplastic molding composition by plotting the Yellowness Index (YI) as a function of the time of heat stress, for the stabilizers Zn/PX ( ⁇ ) and Zn/PX/Cop (*); and
- FIG. 6 graphically illustrates the heat-stabilizing effect of various stabilizers in a thermoplastic molding composition by plotting the Yellowness Index (YI) as a function of the time of heat stress, for the stabilizers Zn/PX/TMP (+) and Zn/PX/TMP/Cop ( ⁇ ).
- YI Yellowness Index
- one aspect of the present invention relates to costabilizers I based on copolymers of ##STR2##
- the compounds of formula I may be synthesized from the compounds of the formulae Ia and Ib in which R 1 is a straight-chain or branched alkyl group having from 1 to 20 carbon atoms, including, e.g , methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl, nonyl, isononyl, decyl, isodecyl, dodecyl, isododecyl, tridecyl, tetradecyl, hexadecyl, octadecyl or arachinyl or is cyclic or alkyl-substituted cycloalkyl group, including, e.g., cyclopentyl, he
- R 1 may also be an alkenyl group having from 3 to 18 carbon atoms, including, e.g., propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, dodecenyl, tetradecenyl, hexadecenyl or octadecenyl.
- R 1 may also represent an alkyl-, halogen-, or hydroxyl-substituted or unsubstituted aryl such as, for example, phenyl, o-tolyl, m-tolyl, p-tolyl, p-tert-butylphenyl, p-nonylphenyl, p-dodecylphenyl, o-hydroxyphenyl, m-hydroxyphenyl, p-hydroxyphenyl, o-chlorophenyl, m-chlorophenyl or p-chlorophenyl.
- aryl such as, for example, phenyl, o-tolyl, m-tolyl, p-tolyl, p-tert-butylphenyl, p-nonylphenyl, p-dodecylphenyl, o-hydroxyphenyl, m-hydroxyphenyl, p-hydroxyphen
- R 1 may also be a straight chain or branched alkoxy group having from 1 to 20 carbon atoms, including, e.g., methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentyloxy, isopentyloxy, hexyloxy, isohexyloxy, heptyloxy, isoheptyloxy, octyloxy, isooctyloxy, nonyloxy, isononyloxy, decyloxy, isodecyloxy, dodecyloxy, isododecyloxy, tridecyloxy, tetradecyloxy, hexadecyloxy, octadecyloxy or arachinyloxy; or cyano; or a straight chain or branched alkoxy group having from 1 to 20 carbon atoms, including, e.g., methyl-, ethyl-,
- X may be a straight chain or branched alkylene group having from 1 to 20 carbon atoms, including, e.g., methylene, ethylene, propylene, isopropylene, butylene, isobutylene, pentylene, isopentylene, hexylene, isohexylene, heptylene, isoheptylene, octylene, isooctylene, nonylene, isononylene, decylene, isodecylene, dodecylene, isododecylene, tridecylene, tetradecylene, hexadecylene, octadecylene or arachinylene or a cyclic or alkyl-substituted cycloalkylene group having 5 to 10 carbon atoms, including, e.g., cyclopentylene, cyclohexylene, cycloheptylene, cyclo
- X may also be an alkenylene group having from 3 to 18 carbon atoms, including, e.g., ethenylene, propenylene, butenylene, pentenylene, hexenylene, heptenylene, octenylene, nonenylene, decenylene, dodecenylene, tetradecenylene, hexadecenylene or octadecenylene.
- alkenylene group having from 3 to 18 carbon atoms including, e.g., ethenylene, propenylene, butenylene, pentenylene, hexenylene, heptenylene, octenylene, nonenylene, decenylene, dodecenylene, tetradecenylene, hexadecenylene or octadecenylene.
- X may also represent an alkyl-, halogen-, cyano, or hydroxyl-substituted or unsubstituted arylene such as, for example, phenylene, o-tolylene, o-nonylphenylene, o-dodecylphenylene, o-hydroxyphenylene, o-chlorophenylene and o-cyanophenylene.
- X may also be a straight chain or branched alkyleneoxy group having from 1 to 20 carbon atoms, including, e.g., methyleneoxy, ethyleneoxy, propyleneoxy, isopropyleneoxy, butyleneoxy, isobutyleneoxy, pentyleneoxy, isopentyleneoxy, hexyleneoxy, isohexyleneoxy, heptyleneoxy, isoheptyleneoxy, octyleneoxy, isooctyleneoxy, nonyleneoxy, isononyleneoxy, decyleneoxy, isodecyleneoxy, dodecyleneoxy, isododecyleneoxy, tridecyleneoxy, tetradecyleneoxy, hexadecyleneoxy, octadecyleneoxy or arachinyleneoxy.
- X may also be a straight chain or branched alkylenecarbonyl group, including, e.g., ethylene-, propylene-, isopropylene-, butylene-, isobutylene-, pentylene-, isopentylene-, hexylene-, isohexylene-, heptylene-, isoheptylene-, octylene-, isooctylene-, nonylene-, isononylene-, decylene-, isodecylene-, dodecylene-, isododecylene-, tridecylene-, tetradecylene-, hexadecylene-, octadecylene- or arachinylene-carbonyl.
- alkylenecarbonyl group including, e.g., ethylene-, propylene-, isopropylene-, butylene-, isobutylene-, pent
- the preparation of the costabilizers I may be carried out by reacting the compounds Ia and Ib in a mole ratio of from 90:10 to 99:1, preferably from 94:6 to 99:1, especially preferably in a ratio of Ia:Ib greater than about 95:5, in particular in about 97.5:2.5 mol%, in ethylbenzene (containing about 95 ppm of water) with catalytic amounts (0.5 to 1.5 mol%, in particular about 0.9 mol%) of methyl 4-toluenesulphonate for a reaction time of about 12 to 15 minutes at 133° C. and a post-polymerization time of 60 minutes at 133° C. This gives a crosslinked copolymer (I) in yields >95%.
- the present invention relates to stabilizer systems which contain the present costabilizer and primary stabilizers based on a zinc compound and polyoxazolines.
- the zinc compound is characterized in that it contains one or more compounds of zinc of the formula
- R 2 and R 3 may be identical or different and represent straight-chain or branched, optionally hydroxyl-substituted aliphatic acyl groups having from 8 to 36 carbon atoms or aryl groups which are optionally substituted by alkyl groups having from 1 to 22 carbon atoms.
- the C 8 -C 21 carboxylic acids are, for example, benzoic acid, p-tert-butylbenzoic acid or aliphatic carboxylic acids, in particular octanoic acid, dodecanoic acid, stearic acid or oleic acid.
- Preferred examples of zinc compounds are zinc soaps of fatty acids having from 8 to 36, preferably from 8 to 22 carbon atoms. Suitable examples of these are in particular caprylates, caprates, laurates, myristates, palmitates, stearates and behenates. It is also possible to use the salts of branched fatty acids such as 2-ethylhexanoic acid, 2-octyldecanoic acid or tetradecyloctadecanoic acid or hydroxy-fatty acids such as 9(10)-hydroxystearic acid or 9,10-dihydroxystearic acid.
- the zinc soaps may be composed of the salts of individual fatty acids or from fatty acid mixtures such as are obtained from natural fats.
- Suitable salts of aromatic carboxylic acids are in particular the zinc salts of benzoic acid and of substituted benzoic esters, in particular of alkyl-substituted benzoic acid.
- Suitable phenolates are: methylphenolates, tert-butylphenolates, nonylphenolates, dodecylphenolates or naphthenates of zinc.
- the polyoxazolines used as primary stabilizers are represented by the following formula: ##STR3## in which R 4 are optionally different, straight-chain or branched alkyl radicals having from 1 to 22 carbon atoms or substituted or unsubstituted cycloalkyl or aryl radicals, preferably alkyl radicals having from 1 to 12 carbon atoms, while n represents integers from 10 to 10,000 (see, e.g.. DE-C-0,253,985).
- Examples of compounds of the formula III are polymethyloxazoline, polyethyloxazoline, poly-n-propyloxazoline, polyisopropyloxazoline, polyundecyloxazoline and polyphenyloxazoline.
- primary stabilizers which can be used are copolymers of two different alkyl- or aryl-oxazolines each being present in a proportion of between 5% and 95%. It is also possible to use terpolymers of three different oxazolines, each being present in a proportion of from 5 to 95%.
- stabilized molding compositions which, in addition to the above-mentioned primary stabilizers (II) and (III), contain compounds of tin, lead or antimony or combinations of compounds of cadmium, barium, calcium and zinc.
- the stabilizer mixtures according to the present invention may be used for stabilizing chlorine-containing polymers.
- These are preferably vinyl chloride homopolymers or vinyl chloride copolymers. Preference is furthermore given to suspension polymers and mass polymers and also to emulsion polymers.
- Suitable comonomers for the copolymers are for example: vinyl acetate, vinylidene chloride, trans-dichloroethene, ethylene, propylene, butylene, maleic acid, acrylic acid, fumaric acid and itaconic acid.
- chlorine-containing polymers are post-chlorinated PVC and chlorinated polyolefins, and also graft copolymers of PVC with ethylene-vinyl acetate (EVA), acrylonitrile-butadienestyrene (ABS) and methacrylate-butadiene-styrene (MBS).
- EVA ethylene-vinyl acetate
- ABS acrylonitrile-butadienestyrene
- MFS methacrylate-butadiene-styrene
- the stabilized molding compositions suitably contain the primary stabilizers of the formula II and III in amounts of from 0.02 to 2.0 percent by weight, in particular of from 0.05 to 1.0 percent by weight of each, based on the weight of the chlorine-containing polymer.
- the costabilizer according to the invention of the formula I is advantageously used in amounts of from 0.001 to 2.0, preferably in amounts of from 0.01 to 0.05 percent by weight, based on the weight of the chlorine-containing polymer.
- the stabilized molding compositions according to the invention may additionally contain commercially available costabilizers. These are, for example, epoxy compounds, preferably epoxidized fatty acids such as epoxidized soya bean oil, phosphites, in particular mixed aryl-alkyl phosphites, and phenolic antioxidants, which are preferably incorporated in amounts of from 0.05 to 5.0, in particular from 0.1 to 3.0 percent by weight, based on the weight of the chlorine-containing polymer.
- costabilizers are, for example, epoxy compounds, preferably epoxidized fatty acids such as epoxidized soya bean oil, phosphites, in particular mixed aryl-alkyl phosphites, and phenolic antioxidants, which are preferably incorporated in amounts of from 0.05 to 5.0, in particular from 0.1 to 3.0 percent by weight, based on the weight of the chlorine-containing polymer.
- Suitable conventional phosphites are phosphites of the general formula IV and V ##STR4## in which R 5 , R 6 and R 7 are identical or different and denote C 6 -C 18 -alkyl, a phenyl radical which may be unsubstituted or substituted by C 1 -C 9 -alkyl or C 1 -C 9 -alkoxy, or denote C 5 -C 7 -cycloalkyl, and in which R 8 is C 5 -C 18 -alkyl.
- R 5 , R 6 , R 7 and R 8 denote C 6 -C 18 alkyl, this is, for example, n-hexyl, n-octyl, n-nonyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl. Preference is given to alkyl groups having from 8 to 12 carbon atoms.
- R 5 , R 6 and R 7 as substituted phenyl, are for example tolyl, ethylphenyl, xylyl, nonylphenyl, cumyl, cresyl, 4-methoxyphenyl, 2,4-dimethoxyphenyl, ethoxyphenyl, butoxyphenyl, p-n-octylphenyl or p-n-nonylphenyl.
- suitable phosphites are trioctyl, tridecyl, tridodecyl, tritetradecyl, tristearyl, trioleyl, triphenyl, tricresyl, tris-p-nonylphenyl and tricyclohexyl phosphite, and particular preference is given to the aryl dialkyl phosphites and also to the alkyl diaryl phosphites such as for example, phenyl didecyl phosphite, nonylphenyl didecyl phosphite, (2,4-di-tert-butylphenyl) didodecyl phosphite and (2,6-di-tert-butylphenyl) didodecyl phosphite.
- antioxidants are alkylated monophenols and hydroquinones, hydroxylated thiodiphenyl ethers, 1,4-alkylidene-bis-phenols, benzyl compounds, acylaminophenols, esters or amides of ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid and esters of ⁇ -(5-tertbutyl-4-hydroxy-3-methylphenyl)propionic acid.
- Preferred antioxidants are alkylated monophenols, alkylidene-bisphenols and phenyl-substituted propionic esters, in particular, 2,6-di-tert-butyl-p-cresol, 2,2-bis(4'-hydroxyphenyl)propane and n-octadecyl ⁇ -(3,5-ditert-butyl-4-hydroxyphenyl)propionate.
- the compound of the formula I can also be used with other nitrogen-containing organic stabilizers.
- these are cyanamide, dicyandiamide, guanamines such as benzoguanamine, indoles such as phenylindole, pyrazoles (for example as described in GB-B-866,936), ureas and thioureas such as monophenylurea and diphenylthiourea, and aminocrotonic esters; also, ⁇ -diketones such as stearylbenzoylmethane, and polyols such as pentaerythritol.
- the stabilized molding compositions according to the invention by conventional methods, for example, by simple mechanical mixing of the components in conventional mixers.
- This mixing operation may be used to incorporate other conventional processing auxiliaries such as for example lubricants (montan waxes or polyol partial esters), plasticizers, fillers, light stabilizers, pigments or other costabilizers such as, for example, epoxidized fatty acid esters.
- the action of various stabilizer combinations was tested by determining the static heat stability of a milled sheet.
- the stabilizer combinations and optionally plasticizers and processing auxiliaries were mixed with polyvinyl chloride for 30 seconds in a laboratory mill and then processed on a two-roll mill at a roll temperature of 170° C., with co-rotation, over the course of 5 minutes to form 1 mm thick milled sheets.
- Strips of dimensions 14 ⁇ 250 mm were cut from the milled sheets, and these strips were then subjected to heat stress in a special oven (Metrastat, type Sigma) at 180° C. Under the test conditions, the test strips were continuously discharged from the heating zone, and the effect of the stabilizers on the color variation was determined.
- the color variations were assessed objectively, and the test strips were compared with each other by determining the yellowness indices (YI; ASTM Method E 313-73) using a colorimeter (LabScan 5100 plus) from Dr. Slevogt & Co. and plotting the yellowness indices against the duration of heat stress. High YI values indicate strong discoloration and thus low stability.
- PC Copolymer of methyl- and isopropyl-oxazoline
- Cop Copolymer of ethyloxazoline and tetramethylene-bis-oxazoline (molar ratio 87,5:2,5)
- K-value 70 100 parts of suspension-polyvinyl chloride (K-value 70; VESTOLIT S 7054; Huls AG, Marl, West Germany)
- K-value 70 100 parts of suspension-polyvinyl chloride (K-value 70; VESTOLIT S 7054; Huls AG, Marl, West Germany)
- K-value 70 100 parts of suspension-polyvinyl chloride (K-value 70; VESTOLIT S 7054; Huls AG, Marl, West Germany)
- K-value 58 100 parts of mass-polyvinyl chloride (K-value 58; VESTOLIT M 5867; Huls AG, Marl, West Germany)
- the polyvinyl chloride molding compositions to be tested were prepared by adding one of the stabilizers given in Table 2 to one of the formulations A to E, and these mixtures were processed in the manner described above to form test strips.
- the results of these tests are summarized in Table 1, and the detailed results for a number of various combinations of chlorine-containing polymer formulation and stabilizer mixture are presented in Examples 1-10 and FIGS. 1 and 12.
- VESTOLIT S 7054 100 parts by wt. of VESTOLIT S 7054
- VESTOLIT S 7054 100 parts by wt. of VESTOLIT S 7054
- VESTOLIT S 7054 100 parts by wt. of VESTOLIT S 7054
- VESTOLIT S 7054 100 parts by wt. of VESTOLIT S 7054
- VESTOLIT S 7054 100 parts by wt. of VESTOLIT S 7054
- VESTOLIT S 7054 100 parts by wt. of VESTOLIT S 7054
- VESTOLIT S 6058 100 parts by wt. of VESTOLIT S 6058
- VESTOLIT S 6058 100 parts by wt. of VESTOLIT S 6058
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Abstract
Costabilizers which are copolymers of oxazolines and bisoxazolines enhance the stabilizing properties of primary stabilizers such as polyoxazolines and zinc compounds in chloride-containing thermoplastic molding compositions, preferably based on polymers of vinyl chloride.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
relates to rigid or plasticized,
The present invention stabilized thermoplastic molding compositions based on halogen-containing polymers, in particular polyvinyl chloride or polymers essentially containing vinyl chloride, and costabilizers for preparing such compositions.
2. Discussion of the Background
It is known that chloride-containing polymers are readily degraded by the action of heat, for example, during processing. This degradation leads to undesired discolorations and to an impairment of the mechanical properties. Consequently, this degradation is avoided by adding stabilizers to the polymers before processing. In the case of polyvinyl chloride and copolymers containing essentially vinyl chloride, particular use is made of organotin compounds, inorganic and organic lead salts, organic antimony compounds or combinations of cadmium carboxylates and barium carboxylates and also of a mixture of zinc soaps and polyoxazolines. These so-called primary stabilizers are frequently supplemented with costabilizers to improve their effectiveness. The modes of action of primary or co-stabilizers and their combined action (synergism) are described in the relevant literature, for example in the publication by L. I. Nass, "Heat Stabilizers", Kirk-Othmer Encyclopedia of Chemical Technology, volume 12, 3rd edition, page 225, published by John Wiley and Sons, 1980.
Essentially, these are costabilizers which improve the initial color and the ultimate stability of the chlorine-containing polymer. For instance, epoxy compounds, polyols, organic phosphites, substituted dihydropyridines, 1,3-diketones or combinations of these compounds are used.
At the present time, there are no highly effective costabilizers for primary stabilizers based on polymers. Therefore, there remains a need for substances or mixtures of substances which enhance or reinforce the heat-stabilizing action of polymeric primary stabilizers.
Accordingly, one object of this invention is to provide costabilizers which enhance the heat-stabilizing action of stabilizers.
It is another object to provide costabilizers which enhance the heat-stabilizing action of primary polymeric stabilizers.
It is another object to provide costabilizers which enhance the heat-stabilizing action of stabilizers used to stabilize halogen-containing polymers.
It is another object to provide novel stabilizer mixtures which stabilize halogen-containing polymers to the action of heat.
It is another object to provide novel stabilized thermoplastic molding compositions which contain a costabilizer which enhances the heat-stabilizing action of stabilizers.
It is another object to provide novel stabilized thermoplastic molding compositions which contain a costabilizer which enhances the heat-stabilizing action of primary polymeric stabilizers.
It is another object to provide novel stabilized thermoplastic molding compositions based on halogen-containing polymers which contain a stabilizer and a costabilizer which enhances the heat-stabilizing action of the stabilizer.
These and other objects, which will become apparent during the following detailed description, have been achieved by the discovery that costabilizers of formula I based on copolymers of ##STR1## greatly improve the stabilizing effect of primary stabilizers.
A more complete appreciation of the invention and many of the attendant advantages thereof will be readily obtained as the same become better understood by reference to the following detailed description when considered in connection with the accompanying drawings, wherein:
FIGS. 1, 7, 10 and 11 graphically illustrate the heat-stabilizing effect of various stabilizers in various thermoplastic molding compositions by plotting the Yellowness Index (YI) as a function of the time of heat stress, for the stabilizers: Zn/PX (·), Zn/PX/TMP (+), Zn/PX/Cop (*) and Zn/PX/TMP/Cop (□);
FIGS. 2, 8, 9 and 12 graphically illustrate the heat-stabilizing effect of various stabilizers in various thermoplastic molding compositions by plotting the Yellowness Index (YI) as a function of the time of heat stress, for the stabilizers: Zn/PC (·), Zn/PC/TMP (+), Zn/PC/Cop (*) and Zn/PC/TMP/Cop (□);
FIG. 3 graphically illustrates the heat-stabilizing effect of various stabilizers in a thermoplastic molding composition by plotting the Yellowness Index (YI) as a function of the time of heat stress, for the stabilizers Zn/PC (·) and Zn/PC/Cop (*);
FIG. 4 graphically illustrates the heat-stabilizing effect of various stabilizers in a thermoplastic molding composition by plotting the Yellowness Index (YI) as a function of the time of heat stress, for the stabilizers: Zn/PC/TMP (+) and Zn/PC/TMP/Cop (□);
FIG. 5 graphically illustrates the heat-stabilizing effect of various stabilizers in a thermoplastic molding composition by plotting the Yellowness Index (YI) as a function of the time of heat stress, for the stabilizers Zn/PX (·) and Zn/PX/Cop (*); and
FIG. 6 graphically illustrates the heat-stabilizing effect of various stabilizers in a thermoplastic molding composition by plotting the Yellowness Index (YI) as a function of the time of heat stress, for the stabilizers Zn/PX/TMP (+) and Zn/PX/TMP/Cop (□).
Thus, one aspect of the present invention relates to costabilizers I based on copolymers of ##STR2##
The compounds of formula I may be synthesized from the compounds of the formulae Ia and Ib in which R1 is a straight-chain or branched alkyl group having from 1 to 20 carbon atoms, including, e.g , methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl, nonyl, isononyl, decyl, isodecyl, dodecyl, isododecyl, tridecyl, tetradecyl, hexadecyl, octadecyl or arachinyl or is cyclic or alkyl-substituted cycloalkyl group, including, e.g., cyclopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl or arachinyl.
Furthermore, R1 may also be an alkenyl group having from 3 to 18 carbon atoms, including, e.g., propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, dodecenyl, tetradecenyl, hexadecenyl or octadecenyl.
Moreover, R1 may also represent an alkyl-, halogen-, or hydroxyl-substituted or unsubstituted aryl such as, for example, phenyl, o-tolyl, m-tolyl, p-tolyl, p-tert-butylphenyl, p-nonylphenyl, p-dodecylphenyl, o-hydroxyphenyl, m-hydroxyphenyl, p-hydroxyphenyl, o-chlorophenyl, m-chlorophenyl or p-chlorophenyl.
R1 may also be a straight chain or branched alkoxy group having from 1 to 20 carbon atoms, including, e.g., methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentyloxy, isopentyloxy, hexyloxy, isohexyloxy, heptyloxy, isoheptyloxy, octyloxy, isooctyloxy, nonyloxy, isononyloxy, decyloxy, isodecyloxy, dodecyloxy, isododecyloxy, tridecyloxy, tetradecyloxy, hexadecyloxy, octadecyloxy or arachinyloxy; or cyano; or a straight chain or branched acyl group having from 1 to 20 carbon atoms, including, e.g., methyl-, ethyl-, propyl-, isopropyl-, butyl-, isobutyl-, pentyl-, isopentyl-, hexyl-, isohexyl-, heptyl-, isoheptyl-, octyl-, isooctyl-, nonyl-, isononyl-, decyl-, isodecyl-, dodecyl-, isododecyl-, tridecyl-, tetradecyl-, hexadecyl-, octadecyl- or arachinyl-carbonyl.
X may be a straight chain or branched alkylene group having from 1 to 20 carbon atoms, including, e.g., methylene, ethylene, propylene, isopropylene, butylene, isobutylene, pentylene, isopentylene, hexylene, isohexylene, heptylene, isoheptylene, octylene, isooctylene, nonylene, isononylene, decylene, isodecylene, dodecylene, isododecylene, tridecylene, tetradecylene, hexadecylene, octadecylene or arachinylene or a cyclic or alkyl-substituted cycloalkylene group having 5 to 10 carbon atoms, including, e.g., cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, cyclononylene, or cyclodecylene.
Moreover, X may also be an alkenylene group having from 3 to 18 carbon atoms, including, e.g., ethenylene, propenylene, butenylene, pentenylene, hexenylene, heptenylene, octenylene, nonenylene, decenylene, dodecenylene, tetradecenylene, hexadecenylene or octadecenylene.
Furthermore, X may also represent an alkyl-, halogen-, cyano, or hydroxyl-substituted or unsubstituted arylene such as, for example, phenylene, o-tolylene, o-nonylphenylene, o-dodecylphenylene, o-hydroxyphenylene, o-chlorophenylene and o-cyanophenylene.
X may also be a straight chain or branched alkyleneoxy group having from 1 to 20 carbon atoms, including, e.g., methyleneoxy, ethyleneoxy, propyleneoxy, isopropyleneoxy, butyleneoxy, isobutyleneoxy, pentyleneoxy, isopentyleneoxy, hexyleneoxy, isohexyleneoxy, heptyleneoxy, isoheptyleneoxy, octyleneoxy, isooctyleneoxy, nonyleneoxy, isononyleneoxy, decyleneoxy, isodecyleneoxy, dodecyleneoxy, isododecyleneoxy, tridecyleneoxy, tetradecyleneoxy, hexadecyleneoxy, octadecyleneoxy or arachinyleneoxy.
X may also be a straight chain or branched alkylenecarbonyl group, including, e.g., ethylene-, propylene-, isopropylene-, butylene-, isobutylene-, pentylene-, isopentylene-, hexylene-, isohexylene-, heptylene-, isoheptylene-, octylene-, isooctylene-, nonylene-, isononylene-, decylene-, isodecylene-, dodecylene-, isododecylene-, tridecylene-, tetradecylene-, hexadecylene-, octadecylene- or arachinylene-carbonyl.
Preference is given to the use of compounds of the formulae Ia and Ib in which R1 is methyl, ethyl or propyl and X is ethylene, trimethylene, tetramethylene or phenylene.
The preparation of the costabilizers I may be carried out by reacting the compounds Ia and Ib in a mole ratio of from 90:10 to 99:1, preferably from 94:6 to 99:1, especially preferably in a ratio of Ia:Ib greater than about 95:5, in particular in about 97.5:2.5 mol%, in ethylbenzene (containing about 95 ppm of water) with catalytic amounts (0.5 to 1.5 mol%, in particular about 0.9 mol%) of methyl 4-toluenesulphonate for a reaction time of about 12 to 15 minutes at 133° C. and a post-polymerization time of 60 minutes at 133° C. This gives a crosslinked copolymer (I) in yields >95%.
In addition to the costabilizer I, the present invention relates to stabilizer systems which contain the present costabilizer and primary stabilizers based on a zinc compound and polyoxazolines. The zinc compound is characterized in that it contains one or more compounds of zinc of the formula
R.sup.2 O--Zn--OR.sup.3 (II)
in which R2 and R3 may be identical or different and represent straight-chain or branched, optionally hydroxyl-substituted aliphatic acyl groups having from 8 to 36 carbon atoms or aryl groups which are optionally substituted by alkyl groups having from 1 to 22 carbon atoms. The C8 -C21 carboxylic acids are, for example, benzoic acid, p-tert-butylbenzoic acid or aliphatic carboxylic acids, in particular octanoic acid, dodecanoic acid, stearic acid or oleic acid.
Preferred examples of zinc compounds are zinc soaps of fatty acids having from 8 to 36, preferably from 8 to 22 carbon atoms. Suitable examples of these are in particular caprylates, caprates, laurates, myristates, palmitates, stearates and behenates. It is also possible to use the salts of branched fatty acids such as 2-ethylhexanoic acid, 2-octyldecanoic acid or tetradecyloctadecanoic acid or hydroxy-fatty acids such as 9(10)-hydroxystearic acid or 9,10-dihydroxystearic acid. The zinc soaps may be composed of the salts of individual fatty acids or from fatty acid mixtures such as are obtained from natural fats. Suitable salts of aromatic carboxylic acids are in particular the zinc salts of benzoic acid and of substituted benzoic esters, in particular of alkyl-substituted benzoic acid. Suitable phenolates are: methylphenolates, tert-butylphenolates, nonylphenolates, dodecylphenolates or naphthenates of zinc.
The polyoxazolines used as primary stabilizers are represented by the following formula: ##STR3## in which R4 are optionally different, straight-chain or branched alkyl radicals having from 1 to 22 carbon atoms or substituted or unsubstituted cycloalkyl or aryl radicals, preferably alkyl radicals having from 1 to 12 carbon atoms, while n represents integers from 10 to 10,000 (see, e.g.. DE-C-0,253,985). Examples of compounds of the formula III are polymethyloxazoline, polyethyloxazoline, poly-n-propyloxazoline, polyisopropyloxazoline, polyundecyloxazoline and polyphenyloxazoline. Other primary stabilizers which can be used are copolymers of two different alkyl- or aryl-oxazolines each being present in a proportion of between 5% and 95%. It is also possible to use terpolymers of three different oxazolines, each being present in a proportion of from 5 to 95%.
Other highly suitable materials are those stabilized molding compositions which, in addition to the above-mentioned primary stabilizers (II) and (III), contain compounds of tin, lead or antimony or combinations of compounds of cadmium, barium, calcium and zinc.
The stabilizer mixtures according to the present invention may be used for stabilizing chlorine-containing polymers. These are preferably vinyl chloride homopolymers or vinyl chloride copolymers. Preference is furthermore given to suspension polymers and mass polymers and also to emulsion polymers. Suitable comonomers for the copolymers are for example: vinyl acetate, vinylidene chloride, trans-dichloroethene, ethylene, propylene, butylene, maleic acid, acrylic acid, fumaric acid and itaconic acid. Other suitable chlorine-containing polymers are post-chlorinated PVC and chlorinated polyolefins, and also graft copolymers of PVC with ethylene-vinyl acetate (EVA), acrylonitrile-butadienestyrene (ABS) and methacrylate-butadiene-styrene (MBS).
The stabilized molding compositions suitably contain the primary stabilizers of the formula II and III in amounts of from 0.02 to 2.0 percent by weight, in particular of from 0.05 to 1.0 percent by weight of each, based on the weight of the chlorine-containing polymer.
The costabilizer according to the invention of the formula I is advantageously used in amounts of from 0.001 to 2.0, preferably in amounts of from 0.01 to 0.05 percent by weight, based on the weight of the chlorine-containing polymer.
The stabilized molding compositions according to the invention may additionally contain commercially available costabilizers. These are, for example, epoxy compounds, preferably epoxidized fatty acids such as epoxidized soya bean oil, phosphites, in particular mixed aryl-alkyl phosphites, and phenolic antioxidants, which are preferably incorporated in amounts of from 0.05 to 5.0, in particular from 0.1 to 3.0 percent by weight, based on the weight of the chlorine-containing polymer.
Suitable conventional phosphites are phosphites of the general formula IV and V ##STR4## in which R5, R6 and R7 are identical or different and denote C6 -C18 -alkyl, a phenyl radical which may be unsubstituted or substituted by C1 -C9 -alkyl or C1 -C9 -alkoxy, or denote C5 -C7 -cycloalkyl, and in which R8 is C5 -C18 -alkyl.
If R5, R6, R7 and R8 denote C6 -C18 alkyl, this is, for example, n-hexyl, n-octyl, n-nonyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl. Preference is given to alkyl groups having from 8 to 12 carbon atoms.
R5, R6 and R7, as substituted phenyl, are for example tolyl, ethylphenyl, xylyl, nonylphenyl, cumyl, cresyl, 4-methoxyphenyl, 2,4-dimethoxyphenyl, ethoxyphenyl, butoxyphenyl, p-n-octylphenyl or p-n-nonylphenyl.
Most particularly, suitable phosphites are trioctyl, tridecyl, tridodecyl, tritetradecyl, tristearyl, trioleyl, triphenyl, tricresyl, tris-p-nonylphenyl and tricyclohexyl phosphite, and particular preference is given to the aryl dialkyl phosphites and also to the alkyl diaryl phosphites such as for example, phenyl didecyl phosphite, nonylphenyl didecyl phosphite, (2,4-di-tert-butylphenyl) didodecyl phosphite and (2,6-di-tert-butylphenyl) didodecyl phosphite.
Examples of antioxidants are alkylated monophenols and hydroquinones, hydroxylated thiodiphenyl ethers, 1,4-alkylidene-bis-phenols, benzyl compounds, acylaminophenols, esters or amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid and esters of β-(5-tertbutyl-4-hydroxy-3-methylphenyl)propionic acid.
Preferred antioxidants are alkylated monophenols, alkylidene-bisphenols and phenyl-substituted propionic esters, in particular, 2,6-di-tert-butyl-p-cresol, 2,2-bis(4'-hydroxyphenyl)propane and n-octadecyl β-(3,5-ditert-butyl-4-hydroxyphenyl)propionate.
The compound of the formula I can also be used with other nitrogen-containing organic stabilizers. Examples of these are cyanamide, dicyandiamide, guanamines such as benzoguanamine, indoles such as phenylindole, pyrazoles (for example as described in GB-B-866,936), ureas and thioureas such as monophenylurea and diphenylthiourea, and aminocrotonic esters; also, β-diketones such as stearylbenzoylmethane, and polyols such as pentaerythritol.
It is observed, with the stabilized molding compositions according to the present invention based on polymers of vinyl chloride which contain a compound of the formula I as costabilizer, that the presence of compound I reinforces the stabilizing action of a primary stabilizer mixture of zinc compounds and polymers from the group of polyoxazolines to an extent which could not have been foreseen. The positive effect of the present costabilizer is seen as an improvement in the initial color and in a prolongation of the ultimate stability.
It is possible to prepare the stabilized molding compositions according to the invention by conventional methods, for example, by simple mechanical mixing of the components in conventional mixers. This mixing operation may be used to incorporate other conventional processing auxiliaries such as for example lubricants (montan waxes or polyol partial esters), plasticizers, fillers, light stabilizers, pigments or other costabilizers such as, for example, epoxidized fatty acid esters.
It is possible to achieve a homogeneous distribution of the stabilizers in PVC, for example with the aid of a two-roll mill at 150° to 200° C.
Other features of the invention will become apparent in the course of the following descriptions of exemplary embodiments, which are given for illustration of the invention and are not intended to be limiting thereof.
The action of various stabilizer combinations was tested by determining the static heat stability of a milled sheet. For this purpose, the stabilizer combinations and optionally plasticizers and processing auxiliaries were mixed with polyvinyl chloride for 30 seconds in a laboratory mill and then processed on a two-roll mill at a roll temperature of 170° C., with co-rotation, over the course of 5 minutes to form 1 mm thick milled sheets. Strips of dimensions 14×250 mm were cut from the milled sheets, and these strips were then subjected to heat stress in a special oven (Metrastat, type Sigma) at 180° C. Under the test conditions, the test strips were continuously discharged from the heating zone, and the effect of the stabilizers on the color variation was determined.
The color variations were assessed objectively, and the test strips were compared with each other by determining the yellowness indices (YI; ASTM Method E 313-73) using a colorimeter (LabScan 5100 plus) from Dr. Slevogt & Co. and plotting the yellowness indices against the duration of heat stress. High YI values indicate strong discoloration and thus low stability.
The following stabilizers were used:
Zn=Zinc stearate
Ba=Barium stearate
PX=Polyethyloxazoline
PC=Copolymer of methyl- and isopropyl-oxazoline
TMP=Trimethylolpropane
Cop=Copolymer of ethyloxazoline and tetramethylene-bis-oxazoline (molar ratio 87,5:2,5)
The formulations were prepared from the following constituents (parts=parts by weight):
100 parts of suspension-polyvinyl chloride (K-value 70; VESTOLIT S 7054; Huls AG, Marl, West Germany)
30 parts of dioctyl phthalate (VESTINOL AH; Huls AG, Marl, West Germany)
0.3 part of montan wax
100 parts of suspension-polyvinyl chloride (K-value 70; VESTOLIT S 7054; Huls AG, Marl, West Germany)
300 parts of dioctyl phthalate (VESTINOL AH; Huls AG, Marl, West Germany)
0.3 part of zinc stearate
0.6 part of barium stearate
100 parts of suspension-polyvinyl chloride (K-value 70; VESTOLIT S 7054; Huls AG, Marl, West Germany)
1.0 part of stearic acid
100 parts of suspension-polyvinyl chloride (K-value 60; VESTOLIT S 6058; Huls AG, Marl, West Germany)
1.0 part of stearic acid
100 parts of mass-polyvinyl chloride (K-value 58; VESTOLIT M 5867; Huls AG, Marl, West Germany)
5.0 parts of epoxidized soya bean oil (Reoplast 39, Ciba-Geigy AG, Bensheim, West Germany)
The polyvinyl chloride molding compositions to be tested were prepared by adding one of the stabilizers given in Table 2 to one of the formulations A to E, and these mixtures were processed in the manner described above to form test strips. The results of these tests are summarized in Table 1, and the detailed results for a number of various combinations of chlorine-containing polymer formulation and stabilizer mixture are presented in Examples 1-10 and FIGS. 1 and 12.
TABLE 1.
______________________________________
Comparison of the results of the heat test, with
and without costabilizer.
______________________________________
stabilizer composition:
Zinc stearate (Zn)
Polyethyloxazoline (PX)
Copolymer of methyloxazoline
(PC)
and isopropyloxazoline
Trimethylolopropane (TMP)
and costabilizer:
Copolymer of ethyloxazoline and
(Cop)
tetramethylene-bis-oxazoline
______________________________________
Zn/PX/Cop Zn/PC/Cop
without with without with
Formulation TMP TMP TMP TMP
______________________________________
S 7054 better inferior better inferior
Stearic acid
S 7054 equal or equal or better
VESTINOL AH better better
Zn stearate
Ba stearate
S 7054 inferior equal better
VESTINOL AH
Montan wax
(corr. to Wax E)
S 6058 better equal better
Stearic acid
M 5867 inferior better inferior
better
Reoplast 39
______________________________________
TABLE 2.
______________________________________
Constituents of the stabilizer compositions in
parts by weight
Stabilizer mixtures
Zn PX PC TMP Cop
______________________________________
Zn/PX 0.2 0.2
Zn/PC 0.2 0.2
Zn/PX/TMP 0.2 0.2 0.5
Zn/PC/TMP 0.2 0.2 0.5
Zn/PX/Cop 0.2 0.2 0.03
Zn/PC/Cop 0.2 0.2 0.03
Zn/PX/TMP/Cop
0.2 0.2 0.5 0.03
Zn/PC/TMP/Cop
0.2 0.2 0.5 0.03
______________________________________
100 parts by wt. of VESTOLIT S 7054
1.0 part by wt. of stearic acid
______________________________________
YI after heat stress (min)
Stabilizers 10 15 20 25 30 35
______________________________________
Zn/PX 22 25 29 34 37 61
Zn/PX/TMP 12 14 17 23 30 36
Zn/PX/Cop 18 21 25 31 37 39
Zn/PX/TMP/Cop 16 17 19 24 30 36
______________________________________
These results are presented graphically in FIG. 1.
100 parts by wt. of VESTOLIT S 7054
1.0 part by wt. of stearic acid
______________________________________
YI after heat stress (min)
Stabilizers 10 15 20 25 30 35 40
______________________________________
Zn/PC 23 25 28 31 35 -- --
Zn/PC/TMP 13 15 17 21 27 31 33
Zn/PC/Cop 21 24 26 31 37 41 --
Zn/PC/TMP/Cop
14 16 19 24 32 36 --
______________________________________
These results are presented graphically in FIG. 2.
100 parts by wt. of VESTOLIT S 7054
30 parts by wt. of VESTINOL AH
0.3 part by wt. of zinc stearate
0.6 part by wt. of barium stearate
______________________________________
YI after heat stress (min)
Stabilizers 10 15 20 25 30 35 40 45 50 55
______________________________________
Zn/PC 12 12 15 20 17 14 15 25 -- --
Zn/PC/TMP 8 9 9 12 16 16 13 14 33 --
Zn/PC/Cop 11 11 12 14 12 12 12 18 -- --
Zn/PC/TMP/Cop
7 7 8 10 14 15 11 10 19 38
______________________________________
The results for Zn/PC and Zn/PC/Cop are presented graphically in FIG. 3 and the results for Zn/PC/TMP and Zn/PC/TMP/Cop are presented graphically in FIG. 4.
100 parts by wt. of VESTOLIT S 7054
30 parts by wt. of VESTINOL AH
0.3 part by wt. of zinc stearate
0.6 part by wt. of barium stearate
______________________________________
YI after heat stress (min)
Stabilizers
10 15 20 25 30 35 40 45 50 55 60
______________________________________
Zn/PX 11 12 13 15 14 13 14 18 32 66 93
Zn/PX/TMP 8 8 9 11 15 15 13 12 20 47 87
Zn/PX/Cop 11 11 13 15 15 14 14 15 21 45 87
Zn/PX/TMP/
9 9 10 12 16 17 14 13 15 34 69
Cop
______________________________________
The results for Zn/PX and Zn/PX/Cop are presented graphically in FIG. 5, and the results for Zn/PX/TMP and Zn/PX/TMP/Cop are presented graphically in FIG. 6.
100 parts by wt. of VESTOLIT S 7054
30 parts by wt. of VESTINOL AH
0.3 parts by wt. of montan wax
______________________________________
YI after heat stress (min)
Stabilizers 10 15 20 25 30 35
______________________________________
Zn/PX 6 6 7 8 9 9
Zn/PX/TMP 5 5 6 7 8 8
Zn/PX/Cop 6 6 7 8 9 9
Zn/PX/TMP/Cop 5 6 6 6 8 9
______________________________________
These results are presented graphically in FIG. 7.
100 parts by wt. of VESTOLIT S 7054
30 parts by wt. of VESTINOL AH
0.3 parts by wt. of montan wax
______________________________________
YI after heat stress (min)
Stabilizers 10 15 20 25 30 35 40
______________________________________
Zn/PC 6 6 7 8 7 11
Zn/PC/TMP 5 5 6 6 7 9 19
Zn/PC/Cop 6 6 6 7 8 7
Zn/PC/TMP/Cop
5 5 5 6 7 8 11
______________________________________
These results are presented graphically in FIG. 8.
100 parts by wt. of VESTOLIT S 6058
1.0 part by wt. of stearic acid
______________________________________
YI after heat stress (min)
Stabilizers 10 15 20 25 30 35
______________________________________
Zn/PC 19 22 25 29 33 59
Zn/PC/TMP 14 16 18 22 33 90
Zn/PC/Cop 19 21 23 27 34 92
Zn/PC/TMP/Cop 13 14 15 18 25 92
______________________________________
These results are presented graphically in FIG. 9.
100 parts by wt. of VESTOLIT S 6058
1.0 part by wt. of stearic acid
______________________________________
YI after heat stress (min)
Stabilizers 10 15 20 25 30 35
______________________________________
Zn/PX 23 25 29 32 38 65
Zn/PX/TMP 14 17 19 22 26 80
Zn/PX/Cop 20 22 25 29 39 82
Zn/PX/TMP/Cop 14 16 18 22 27 79
______________________________________
These results are presented graphically in FIG. 10.
100 parts by wt. of VESTOLIT M 5867
5.0 parts by wt. of Reoplast 39
______________________________________
YI after heat stress (min)
Stabilizers 10 15 20 25 30 35 40 45
______________________________________
Zn/PX 8 8 9 11 14 18 28
Zn/PX/TMP 8 8 8 10 12 12 15 23
Zn/PX/Cop 8 9 10 12 15 19 33
Zn/PX/TMP/Cop
7 7 7 9 11 11 14 22
______________________________________
These results are presented graphically in FIG. 11.
100 parts by wt. of VESTOLIT M 5867
5.0 parts by wt. of Reoplast 39
______________________________________
YI after heat stress (min)
Stabilizers 10 15 20 25 30 35 40 45 50 55
______________________________________
Zn/PC 9 10 11 13 13 20 34 47 59 69
Zn/PC/TMP 8 8 8 9 12 13 16 24 33 45
Zn/PC/Cop 9 10 12 14 17 19 27 49 67 79
Zn/PC/TMP/Cop
6 7 7 8 10 14 14 20 32 44
______________________________________
These results are presented graphically in FIG. 12.
Obviously, numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that, within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.
Claims (6)
1. A stabilized thermoplastic molding composition, comprising a halogen-containing polymer, a primary stabilizer and costabilizer, wherein said costabilizer is a copolymer I of ##STR5## wherein R1 is a straight-chain or branched alkyl group having from 1 to 20 carbon atoms, a cyclic and/or alkyl-substituted cyclic alkyl group having from 5 to 10 carbon atoms, a straight-chain or branched alkenyl group having from 3 to 18 carbon atoms, an alkyl-, halogen-, or hydroxyl-substituted aryl group, a straight-chain or branched alkoxyl group having from 1 to 20 carbon atoms, a straight-chain or branched alkylcarbonyl group having from 1 to 20 carbon atoms, or a cyano group;
X is a straight-chain or branched alkylene group having from 1 to 20 carbon atoms, a cyclic and/or alkyl-substituted cyclic alkylene group having from 5 to 10 carbon atoms, a straight-chain or branched alkylene group having from 3 to 18 carbon atoms, an alkyl-, halogen-, cyano- or hydroxyl-substituted arylene group, a straight-chain or branched alkyleneoxy group having from 1 to 20 carbon atoms, or a straight-chain or branched alkylenecarbonyl group having from 1 to 20 carbon atoms;
and said primary stabilizer comprises (a) a compound of zinc of the formula (II)
R.sup.2 O--Zn--OR.sup.3 (II)
wherein R2 and R3 are identical or different and represent a straight-chain or branched, optionally hydroxyl-substituted aliphatic acyl group having from 8 to 21 carbon atoms or an aryl group which is optionally substituted by an alkyl group having from 1 to 22 carbon atoms,
and (b) at least one polymeric primary stabilizer selected from the group of polyoxazolines of the formula (III) ##STR6## wherein each occurrence of R4 may independently be a straight-chain or branched alkyl group having from 1 to 22 carbon atoms or a substituted or unsubstituted cycloalkyl or aryl group, and n represents an integer of from 10 to 10,000.
2. The stabilized molding composition of claim 1, wherein said copolymer I is present in an amount of from 0.001 to 2.0 percent by weight and the compounds of the formulae II and III are each present in an amount of from 0.02 to 2.0 percent by weight, based on the weight of the halogen-containing polymer.
3. The stabilized molding composition of claim 1, further comprising an additional primary stabilizer in the form of a compound of tin, lead or antimony or a combination of compounds of cadmium, barium, calcium and zinc and an additional costabilizer selected from the group consisting of phosphites, 1,3-diketones, polyols, alkylated phenols, cyanamides, dicyandiamides, guanamines, indoles, pyrazoles, ureas, thioureas, monophenylureas, diphenylthiourea and aminocrotonic esters.
4. The molding composition of claim 1, wherein R4 is an alkyl group having from 1 to 12 carbon atoms.
5. A stabilizer mixture, comprising an (a) primary stabilizer which comprises an (i) compound of the formula (II)
R.sup.2 O--Zn--OR.sup.3 (II)
wherein R2 and R3 are identical or different and represent a straight-chain or branched, optionally hydroxyl-substituted aliphatic acyl group having from 8 to 21 carbon atoms or an aryl group which is optionally substituted by an alkyl group having from 1 to 22 carbon atoms,
and (ii) at least one polymeric primary stabilizer selected from the group of polyoxazolines of the formula (III) ##STR7## wherein each occurrence of R4 may independently be a straight-chain or branched alkyl group having from 1 to 22 carbon atoms or a substituted or unsubstituted cycloalkyl or aryl group, and n represents an integer of from 10 to 10,000; and
(b) a costabilizer which is a copolymer I of ##STR8## wherein R1 is a straight-chain or branched alkyl group having from 1 to 20 carbon atoms, a cyclic and/or alkyl-substituted cyclic alkyl group having from 5 to 10 carbon atoms, a straight-chain or branched alkenyl group having from 3 to 18 carbon atoms, an alkyl-, halogen- or hydroxyl-substituted aryl group, a straight-chain or branched alkoxy group having from 1 to 20 carbon atoms, a straight-chain or branched alkylcarbonyl group having from 1 to 20 carbon atoms, or a cyano group;
X is a straight-chain or branched alkylene group having from 1 to 20 carbon atoms, a cyclic and/or alkyl-substituted cyclic alkylene group having from 5 to 10 carbon atoms, a straight-chain or branched alkylene group having from 3 to 18 carbon atoms, an alkyl-, halogen-, cyano- or hydroxyl-substituted arylene group, a straight-chain or branched alkyleneoxy group having from 1 to 20 carbon atoms, or a straight-chain or branched alkylenecarbonyl group having from 1 to 20 carbon atoms.
6. The stabilizer mixture of claim 5, wherein R4 is an alkyl group having from 1 to 12 carbon atoms.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3932041A DE3932041A1 (en) | 1989-09-26 | 1989-09-26 | POLYMER COSTABILIZERS FOR MOLDS BASED ON VINYL CHLORIDE POLYMERS |
| DE3932041 | 1989-09-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US5063262A true US5063262A (en) | 1991-11-05 |
Family
ID=6390187
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/588,938 Expired - Fee Related US5063262A (en) | 1989-09-26 | 1990-09-26 | Polymeric costabilizers for molding compositions based on polymers of vinyl chloride |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5063262A (en) |
| EP (1) | EP0419793A1 (en) |
| JP (1) | JPH03131647A (en) |
| CA (1) | CA2026084A1 (en) |
| DD (2) | DD298123A5 (en) |
| DE (1) | DE3932041A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040092708A1 (en) * | 2002-06-25 | 2004-05-13 | Bernard Gordon | Graft copolymers and method to prepare same |
| US20060270765A1 (en) * | 2003-04-17 | 2006-11-30 | Wolfgang Wehner | Novel stabilizer system for halogenous polymers |
| US10822569B2 (en) | 2018-02-15 | 2020-11-03 | Afton Chemical Corporation | Grafted polymer with soot handling properties |
| US10851324B2 (en) | 2018-02-27 | 2020-12-01 | Afton Chemical Corporation | Grafted polymer with soot handling properties |
| US10899989B2 (en) | 2018-10-15 | 2021-01-26 | Afton Chemical Corporation | Amino acid grafted polymer with soot handling properties |
| US11046908B2 (en) | 2019-01-11 | 2021-06-29 | Afton Chemical Corporation | Oxazoline modified dispersants |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102017002454A1 (en) * | 2017-03-14 | 2018-09-20 | Friedrich-Schiller-Universität Jena | Organic polymer particles containing poly (oxazoline) stabilizers and use of poly (oxazolines) for the stabilization of organic polymer particles |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4755549A (en) * | 1986-07-17 | 1988-07-05 | Huels Aktiengesellschaft | Stabilized molding compounds based on polyvinyl chloride or vinyl chloride copolymers and stabilizer system |
-
1989
- 1989-09-26 DE DE3932041A patent/DE3932041A1/en not_active Withdrawn
-
1990
- 1990-07-25 EP EP90114243A patent/EP0419793A1/en not_active Withdrawn
- 1990-09-24 CA CA002026084A patent/CA2026084A1/en not_active Abandoned
- 1990-09-25 DD DD90344176A patent/DD298123A5/en not_active IP Right Cessation
- 1990-09-25 DD DD90344175A patent/DD298122A5/en not_active IP Right Cessation
- 1990-09-26 JP JP2254390A patent/JPH03131647A/en active Pending
- 1990-09-26 US US07/588,938 patent/US5063262A/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4755549A (en) * | 1986-07-17 | 1988-07-05 | Huels Aktiengesellschaft | Stabilized molding compounds based on polyvinyl chloride or vinyl chloride copolymers and stabilizer system |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040092708A1 (en) * | 2002-06-25 | 2004-05-13 | Bernard Gordon | Graft copolymers and method to prepare same |
| US7030202B2 (en) * | 2002-06-25 | 2006-04-18 | Polymer Chemistry Innovations, Inc. | Graft copolymers and method to prepare same |
| US20060270765A1 (en) * | 2003-04-17 | 2006-11-30 | Wolfgang Wehner | Novel stabilizer system for halogenous polymers |
| US20090170988A1 (en) * | 2003-04-17 | 2009-07-02 | Crompton Vinyl Additivesgmbh | Stabilizing system for halogenous polymers |
| US10822569B2 (en) | 2018-02-15 | 2020-11-03 | Afton Chemical Corporation | Grafted polymer with soot handling properties |
| US10851324B2 (en) | 2018-02-27 | 2020-12-01 | Afton Chemical Corporation | Grafted polymer with soot handling properties |
| US10899989B2 (en) | 2018-10-15 | 2021-01-26 | Afton Chemical Corporation | Amino acid grafted polymer with soot handling properties |
| US11046908B2 (en) | 2019-01-11 | 2021-06-29 | Afton Chemical Corporation | Oxazoline modified dispersants |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2026084A1 (en) | 1991-03-27 |
| EP0419793A1 (en) | 1991-04-03 |
| JPH03131647A (en) | 1991-06-05 |
| DD298122A5 (en) | 1992-02-06 |
| DE3932041A1 (en) | 1991-04-04 |
| DD298123A5 (en) | 1992-02-06 |
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